Control of phytopathogenic fungi with n-benzothiazae-2-yl n-{40 {11 propylure

ABSTRACT

Phytopathogenic fungi are controlled by the use of compounds of the formula   IN WHICH R9 is C3 alkyl.

United States Patent [191 J aniak [11-], 3,810,988 [4 1 May 14,1974

[ CONTROL OF PHYTOPATHOGENIC FUNGI WITH N-BENZOTHIAZAE-Z-YL N-'PROPYLURE [62] Diviaion of Ser. No. 868,589. Oct, 22, [969, Pat. NO.

[30] Foreign Application Priority Data Nov. 1, I968 Switzerland1633,3/68

52 us. CI. 424/270 [51] Int. Cl....f. AOln 9/12, AOln 9/22 [58] Field 0:Search 424/270 [56] References Cited UNITED STATES PATENTS 2,756,135 77/l956 Searle 260/305 3,551,441 12/1970 Zakaria 260/305 PrimaryExaminerAlbert T. Meyers Assistant Examiner-Allen J. RobinsonAtt0rney,'Agent, or Firm-Frederick H. Rabin 5 7] ABSTRACTPhytopathogenic fungi are controlled by the use of compounds of theformula in which R is C alkyl.

.4 Claims, No Drawings CONTROL OF PHYTOPATHOGENIC FUNGI WITHN-BENZOTHIAZAE-Z-YL N-' PROPYLURE This is a division of application Ser.No. 868,589,

filed on Oct. 22, 1969, now US. Pat. No. 3,725,428.

The present invention provides microbiocidal agents which comprise, asthe active ingredient, a compound of general formula in which Y Y Y andY each represent a hydrogen or halogen atom, an alkyl, alkoxy,alkylthio, carboxyl, carboxyalkyl, nitrile, thiocyanato, nitro,sulphonic acid, sulphonic acid amide, monoalkylsulphonic acid amide,dialkylsulphonic acid amide or optionally substituted phenyl residue, Rrepresents a hydrogen atom or an alkyl residue, R represents the groupOR NHR., or N(R )(R R represents an' alkyl, alkehyl, alkinyl oroptionally substituted phenyl residue, R, represents a hydrogen atom oran alkyl residue, R

represents an alkyl, cycloalkyl, alkenyl, alkinyl, alkoxy or optionallysubstitutedphenyl residue and R and R together with the N-atom to whichthey are linked form a 3-membered to 7-membered heterocyclic ring, withthe proviso that if R represents a methylresidue, one of thesubstituents, Y Y Y and Y, is other than a hydrogen atom, optionallytogether with a liquid or solid carrier or other additive.

The alkyl, alkenyl, alkinyl, alkoxy or alkylthio residues which Y to Y RR R and R may represent, contain one to 18 or two to 18 (in the case ofthe alkenyl or alkinyl residues), but preferably one to four or two tofour carbon atoms. These residues may be branched or straight-chain,unsubstituted or substituted. The cycloalkyls preferably contain threeto si carbon atoms in the ring.

As halogen atoms there may be mentioned F, Cl, Br and Iatoms. Possible Calkyl, C alkenyl and C alkinyl residues are preferably, for example,methyl, trifluo romethyl, ethyl, propyl, isopropyl, n-, i-, sec.- ortert.-butyl, allyl, methylallyl, chlorallyl, methylpropenyl, propinyl oriso-butinyl residues.

The substituents on the alkyl, alkenyl, alkinyl, alkylene, alkoxy,alkylthio and phenyl residues may be of the first order or of the secondorder. By substituents of the first order there are here to beunderstood electron donors which increase the basicity. Here possiblegroups are, amongst others: halogen atoms such as fluorine, chlorine,bromine, or iodine atoms, alkoxy and alltyltl io groupswith oneto fo urcarbon atorns which may be Branched or unbranehedisursimrssiyare 1Hbranched and possess one to two carbon atoms, lower alkoxyalkylenegroups of'the definitions given above, primary. secondary and especiallytertiary amino groups, with lower alkyl and alkanolgroups being pren, ofidentical or different halogen atoms, C alkyl,

C alkoxy, C alkylthio, carboxy C alkyl or nitro groups, n is an integerof 1 to 4, R represents a C alkyl, C alkenyl or optionally substitutedphenyl residue, R and R each represents a C alkyl residue or a3-membered to G-membered cycloalkyl residue, R

represents a C alkyl residue or an optionally substituted phenylresidue. 4

As examples of suitable compounds of formulae I t Compounds of specialimportance are those of for- R R R R' R with a second reagent B, so thatY to Y have the OCH3 H i meanings given for formula I, whilst one of thesubstitu- Q ents A or B represents an amine component -NHCH20CH3 C1 H HH NHCHz-CHS 01 H H H I 0cm 01 H H H N HoH 0cm I 00m H H H inwhich one orboth free valencies are bonded to H. CH to the extent that they are notconstituents of a primary or secondary amine, whilst the otherrepresents the grouping NHCH2OCH3 H H OCH; H NH-CH2CNB H H O CH; H

/OCH3 H H OCHa H I I I NHCH :I1IVS3OOR, I IC0-hal0gen, N-CONH OCH3 OCH;H H OCH; H NHCH' 7 or N=C=O, wherein R can be an easily removable CH3residue which contains C or A represents NH or I I I NH CHaOCH3 H HOCZHS H -NHl2 and B represent the grouping ClCOOR NH-CHr-CNS H H OCZHB Hwherem R has the meaning given for formula I.

The com ounds offormula I can referabl be manu- OCH; H H 00% H P P yfactured: l I I Y a. By reaction of an aromatic residue OCH; #4..

OCH: H H OCzHs H --NHCH --NHCHzCHzOCHa H H H H NH-CH'z-CHOCH3 H H 00H; HN 'NHCHzCHzOCH H H OCQH; H Y -NHCH2CHzOCHa 01 H H H NHCH2CH2OC2H5 H IIOCH; H "A -NH--CH CH OC- H H H 002115 H -NH--CH2CHOC;H; 01 H H H a OCH;H H 002m H Y4 NHC n OQHQ 40 -NH-CHz-CNS H H 00am H -NH-OHz-OHz- CNS Cl HH H NH CHz-OHrCNS H H OOH: H NHCH2-CHz-ONS H H 002E; H with a primary orsecondary amine of formulae NHCH2OCH3 H H OCzHs H .NHCH CNO 01 H H H''NH'CH2GNO H H 00211 1-1 NH'-CH;CNO H H H H --NHCH2CNO H H OCHa H HgNThe present invention also provides the phenylu reas P f P E 5 a; They mmanufactured accord HNR which both together can form the urea groupmg to0 h are t m known for ing, so that therein Y to'Y R and R have themeanample b reactwn of an aromatlc res'due ings given for formula I,whilst A represents the grouping 3| N I I 1| r- 99Yz TPTT W95? .i iTQPTH" alkyl or aryl, and R has the meaning given for formula I.

b. By reaction of an amine of formula with one of the compounds offormulae R N C 0, R aryl. Herein Y, to Y,,, R, and R have the meaningsgiven for formula I.

c. By reaction of an amine of formula.

with a compound of formula Hal-l'i-ORa.

Erysiphe cichoracearum DC., Alternaria tenius or solani, Uromycesphaseoli Pers. Piricularia oryzae Bri. et Cav. and Botrytis cinereaPers. The invention'relates to the use of the compounds of formula I asactive ingredients in microbiocidal preparations.

The preparations according to the invention contain, in addition to theactive ingredient of formula I, a suitable carrier and/or otheradditives. Suitable carriers and additives can be solid. or liquid andcorrespond to the substances which are usual in formulation technologysuch as, for example, natural or regenerated min- 1 eral substances,solvents, diluents, dispersing agents, emulsifiers, wetting agents,adhesives, thickeners, binders or fertilisers. Furthermore, yet furtherbiocidal compounds can be added. Such biocidal compounds can, forexample, belong to the class of the ureas, the saturated or iunsaturated halogenobenzonitriles, halogenobenzoic acids,phenoxyalkylcarboxylic acids, carbamates, triazines, nitroalkylphenols,organic phosphoric acid compounds, quaternary ammonium salts, sulphamicacids, arsena'tes, arsenites, borates or chlorates. Thus, there arenumerous use forms for the new active substances, and these forms willbe dealt with in moredetail below: possible materials for themanufacture of directly sprayable solutions of the compounds of generalformula l are, for example, mineral oil frac' tions of high to mediumboiling range, such as diesel oil or kerosene, coal tar oils and oils ofvegetable or animal origin, as well as hydrocarbons such as alkylatednaphthalenes, tetrahydronaphthalene, xylenes, cyclohexanol, ketone andalso chlorinated hydrocarbons such as trichlorethane andtetrachlorethane, trichlorethylene or trichlorobenzenes andtetrachlorobenzenes, individually or in mutual combination. Solvents ofwhich the boiling point lies above 100C are advantageously used.

Aqueous application formsare especially appropri ately prepared fromemulsion concentrates, pastes or wettable spraying powders by addingwater. Possible emulsifiers or dispersing agents are n'oi1ionicproducts, for example, condensation productsof aliphatic alcohols,amines or carboxylic acids having a long-chain hydrocarbon residue ofabout 10 to 20 carbon atoms with ethylene oxide, such as thecondensation product of octadecylalcohol and 25 to 30 mols of ethyleneoxide, or that of soya fatty acid and 30 mols of ethylene oxide or thatof technical oleylamine and 15' mols of ethylene oxide or that ofdodecylmercaptan and i2 mols of ethylene oxide. Amongst the anionicemulsifiers which can be employed there may be mentioned: the sodiumsalt of dodecyl alcohol sulphuric acid ester, the sodium salt ofdodecylbenzenesulphonic acid, the potassium or triethanolamine salt ofoleic acid or of abietic acid or of mixtures of these acids or thesodium salt of a petroleum, sulphonic acid. Possible cationic dispersingagents are quaternary ammonium compounds such as cetylpyridiniumbromide, or dihydroxyethylbenzyldodecylammonium chloride.

In order to manufacture dusting agents and scattering agents, it ispossible to employ talc, kaolin, bentonite, calciumcarbonate, calciumphosphate, but also charcoal, cork powder, wood flour and othermaterials of 1 vegetable origin as solid carriers. It is also veryappropriate to manufacture the preparations in a granular form. Thevarious use forms can be provided in the usual manner with additions ofsubstances which improve the distribution, adhesion, rain resistance orpenetrating power; as-such substances there may be mentioned: fattyacids, resins, glue, casein or alginates.

In many cases the use of granules for the uniform release of activesubstances over a longer period of time is of advantage. These-granulescan be manufactured by dissolving the active substance in an organicsolvent, absorbing this solution by means of a granular material, forexample, attapulgite or SiO and removing the solvent. They can also bemanufactured by mixing the active substances of formula I withpolymerisable compounds, after which a polymerisation is carried outwhich leaves the active substances unaffected, with the granulationbeing carried out whilst the polymerisation is still proceeding. Thecontent of active substance in the agents described above is between0.01 and percent and it should be mentioned in this context that onapplication from aircraft or by means of other suitable applicationequipment concentrations of up to 99.5

8 EXAMPLE 2 Manufacture of the compound of formula percent oreven pureactive substance are employed. The following Examples illustrate theinvention: 5 a

NH-CON EXAMPLE 1 H5C2O \s a Manufacture of the compound of formula Sixtyml of pyridine are cooled to C and mixed 58.2 g (0.3 mol) of2-amino-6-ethoxybenzthiazole are suspended in 450 ml of dry benzene andheated to 80C, whereupon the substance dissolves. ml of me- 2thylisocyanate are added dropwise to this temperature.

After about 12 ml 'of methylisocyanate have been added dropwise, aprecipitate begins to separate out. Thereafter the mixture is stirredfor a further 2 hours at 80C and then cooled to 5C, and the product isfiltered off. This is immediately obtained in an analytically pure form.Melting point: 222224C. Yield: 73 g 97 N RII Melting Compound ointnumber R R R" Rm R C.)

H H H H 145-4 H H H H 180-18 H H H H 132-3 H H H H 80-85 H H H H 100-10--NH-n(CaHi7) H H H 'H 97-9 NH-CH H H H H 185-8 NHCZH OCHa H H H 145-48-NHC1H OCHz H H 01 183-8 NHCH; H II H 249-5 13 -NHCzH OC2H5 H H H 179-8114 --NHCzH H H C1 H 260 15. -NHC 5 H H -.-OCH; H 300 16. -NHCH3 -OCHz HH CH 220-24 17. --NHCHz OCHa H H H 20143 NHCH3 OC:H5 H H H 243-47 NHCH-CHa H H 01 I 275 --NHCH3 -OC7H5 H H --0C2H5 200-202 --NHCHa OC2H5 H H248-50 NHCH -01 H H H e 255 NHCH3 -CH; H H CH 25 NHCHa H H O H 256- 25NHCH3 H H -O CH H 297-298 26... NHCHa H H H 270 27... NHOHQ H H -OC:H H222-24 28... NHCHa H H CH H 270- 29... NH-n(CaH1) H -CH3 NO: 209-12-NH-n (C H1) O CzHu H H -0C2H5 1 56-58 31... NH-n (C H7) H H (I) 181-83iJ-O C2H 32 NH-n(CaH1 -0CH3 H H -CH 171-73 33... -NH-n(CaH1 --OCHr H H.H -85 34... -NH-n(C;;H -0C'Hz H 01 1 35. NH-n(Ca 1 H --OCH3 H 163-65 36.NH-n(C H1) C1 H H 198-99 37. NH-n(0a 7) 0 CzHs H H 169-71 38.-NH-!1(C3H7) H H -0 C2H5 H 166-67 39. -NH-1 (03117) H H O CzHa H 180-8440. Ha H H -0 CH3 H 210-215 41... N CHa)a H H SCH:4 H -107 42," -N CHagzH H C1 H I 210 43... N CHs a H H CH3 H 181 CH3 v H H 0 C211; H 173-75Decomposition.

EXAMPLE 3 Manufacture of the compound of formula Compound No. 45

45.6 g [0.3 mol] of 2-amino-benzthiazole are dis- -Continued 25 parts ofBolus alba (kaolin) L parts of sodiuml-benzyl'Z-StearyJ-benzirnidagole-oj '-disulphonate 3.5 parts of areaction product of p le".

octylphenol and ethylene oxide.

Emulsion Concentrate Easily soluble active substances can also be formulated as an emulsion concentrate in accordance with solved in 450 ml ofdry ethyl acetate and mixed with 24 the following instruction:

ml of dry pyridine. 36 g of chloroformic acid ethyl ester are addeddropwise at room temperature. The mixture is finally stirred overnight,and the organic phase is washed in a separating funnel with water, so-

dium bicarbonate solution and saturatedsodium chlorl5 idesolution untilneutral, dried over sodium sulphate and evaporated to dryness underreduced pressure. Melting point l98-200C (from alcohol); yield: 62 g91%.

The following compounds of general formula are manufactured analogously.

. parts of active substance parts of xylene and I0 parts of a mixture ofa reaction product of an alkylphenol with ethylene oxide and calciumdodecylbenzenesulphonate are mixed. On dilution with water to thedesired concentration, a sprayable emulsion is produced. Granules 7.5 gof one of the active ingredients of formula I are dissolved in ml ofacetone and the acetone solutionthus obtained is applied to'92 g ofgranulated attapulgite (mesh size: 24/48 meshes/inch). The whole is wellmixed and the solvent is stripped off in a rotational evaporator. Agranular material containing 7.5 percent of active ingredient isobtained.

I EXAMPLES fv isi slT i Melting Compound r olnt Number R R" R R' R 0.

46..-; O H H -002H5 H 2s7 47 O H H H H 195-97 48 /CHa H H H H 185-87-OCH CHs -OC4H n H H1 H H 158-60 OCH2-CHECH2 H H H H 183-85 ./CH3 H H HH 176-78 0-oHt-oH CH3 a2 0OH:-CHz-Br H H a H H mes-1s CH: H H 0C2Hs H230-32 -OCH: H H -o1 H 299 --0 CH1; H H H H -210 -0C2H5 H H OC2H5 H 193F95 .-.,:.?sn22 t 9 a. Cucumber mildew (Erysiphe cichoracearum D.G.)

EXAMPLE 4 DustingAgents Equal parts of an active ingredient of theinvention and precipitated silica are finely ground. Dusting agentspreferably containing 1 to 6 percent of active ingredient can bemanufactured therefrom by mixing 60 with kaolin or talc. SprayingPowders In order to manufacture a spraying powder, the followingcomponents are, for example, mixed and finely ground:

50 parts of an active ingredient of the present invention 20 parts ofHISlL (highly adsorbent silica) 55 Cucumber plants were grown in agreenhouse and sprayed once prophylactically with aqueous sprayingbroths each containing 0.1 percent of the test active substances. Twodays thereafter the plants. treated in choriacearum DC. After 12 to 14days subsequent incubation in the greenhouse, the treated plants were.examined for fungal-attack.

this way were infected with spores of Erysiphe ci-- Results ActiveSubstance No. "/1 Fungal Attack amined for fungal attack.

Results Active Substance No. "/l. Fungal Attack The untreated controlplants were 100 attacked by fungi.

c. Grey rot (Botrytis cinerea Pers.)

Freshly cut vine leaves of the Riesling and Sylvaner variety are sprayedwith aqueous broths each containing 0.1 percent of the testactive'ingredients. After drying the spray deposit, the leaves areinfected with an aqueous conidia suspension of Botrytis cinerea Pets.and incubated in a humidity dish. After .4 days the treated vine leavesare examined for fungal attack.

Results Active Substance No. 7: Fungal Attack The untreated leaves werelOOpercent attacked by fungi. i

I claim:

1. A method for controlling phytopathogenic fungi which comprisesapplying to an area infested with said fungi, a fungicidally effectiveamount ofa compound of the formula I wherein R is C alkyl.

2. The method of claim 1 wherein R is n-propyl. 3. The method of claim 1wherein R is isopropyl. 4. A fungidical composition comprising (l) afungicidally effective amount of a compound of the formula wherein R isC alkyl, and (2) a suitable carrier.

l l l l

2. The method of claim 1 wherein R9 is n-propyl.
 3. The method of claim1 wherein R9 is isopropyl.
 4. A fungidical composition comprising (1) afungicidally effective amount of a compound of the formula